Infrared Spectroscopy Basics

IR Spectroscopy

I.

Introduction A. Spectroscopy is the study of the interaction of matter with the electromagnetic spectrum
1. 2. 3. Electromagnetic radiation displays the properties of both particles and waves The particle component is called a photon The energy (E) component of a photon is proportional to the frequency . Where h is Plancks constant and n is the frequency in Hertz (cycles per second) E = hn 4. The term photon is implied to mean a small, massless particle that contains a small wave-packet of EM radiation/light we will use this terminology in the course

IR Spectroscopy

I.

Introduction 5. Because the speed of light, c, is constant, the frequency, n, (number of cycles of the wave per second) can complete in the same time, must be inversely proportional to how long the oscillation is, or wavelength:

n=

c ___ l

E = hn =
c = 3 x 1010 cm/s

hc ___ l

6. 7.

Amplitude, A, describes the wave height, or strength of the oscillation Because the atomic particles in matter also exhibit wave and particle properties (though opposite in how much) EM radiation can interact with matter in two ways: Collision particle-to-particle energy is lost as heat and movement Coupling the wave property of the radiation matches the wave property of the particle and couple to the next higher quantum mechanical energy level

IR Spectroscopy

I.

Introduction 8. The entire electromagnetic spectrum is used by chemists: Frequency, n in Hz

~1019 ~1017 ~1015 ~1013 ~1010 ~105

Wavelength, l
~.0001 nm ~0.01 nm 10 nm 1000 nm 0.01 cm 100 m

Energy (kcal/mol)
> 300 300-30 300-30 ~10-4 ~10-6

g-rays
nuclear excitation (PET)

X-rays
core electron excitation (X-ray cryst.)

UV
electronic excitation (p to p*)

IR
molecular vibration

Microwave
molecular rotation

Radio
Nuclear Magnetic Resonance NMR (MRI)

Visible

IR Spectroscopy

I.

Introduction C. The IR Spectroscopic Process 1. The quantum mechanical energy levels observed in IR spectroscopy are those of molecular vibration 2.
3.

We perceive this vibration as heat

When we say a covalent bond between two atoms is of a certain length, we are citing an average because the bond behaves as if it were a vibrating spring connecting the two atoms For a simple diatomic molecule, this model is easy to visualize:

4.

IR Spectroscopy

I.

Introduction C. The IR Spectroscopic Process 5. There are two types of bond vibration: Stretch Vibration or oscillation along the line of the bond
H C H
symmetric

H C H
asymmetric

Bend Vibration or oscillation not along the line of the bond

H C H C H
rock
in plane

H C H
twist

H C

H
scissor

H
wag out of plane

Infrared Spectroscopy

C.The IR Spectroscopic Process 6.As a covalent bond oscillates due to the oscillation of the dipole of the molecule a varying electromagnetic field is produced

7.The greater the dipole moment change through the vibration, the more intense the EM field that is generated

Infrared Spectroscopy

C. The IR Spectroscopic Process 8.When a wave of infrared light encounters this oscillating EM field generated by the oscillating dipole of the same frequency, the two waves couple, and IR light is absorbed

9.The coupled wave now vibrates with twice the amplitude

IR beam from spectrometer

coupled wave

EM oscillating wave from bond vibration

Infrared Spectroscopy

D.

The IR Spectrum 1. Each stretching and bending vibration occurs with a characteristic frequency as the atoms and charges involved are different for different bonds
The y-axis on an IR spectrum is in units of % transmittance In regions where the EM field of an osc. bond interacts with IR light of the same n transmittance is low (light is absorbed) In regions where no osc. bond is interacting with IR light, transmittance nears 100%

IR Spectroscopy

D.

The IR Spectrum 2. The x-axis of the IR spectrum is in units of wavenumbers, n, which is the number of waves per centimeter in units of cm-1 (Remember E = hn or E = hc/l)

IR Spectroscopy

D.

The IR Spectrum 3. This unit is used rather than wavelength (microns) because wavenumbers are directly proportional to the energy of transition being observed

chemists like this, physicists hate it

is quicker to understand than

High frequencies and high wavenumbers equate higher energy

Short wavelengths equate higher energy
4. 5. 6. This unit is used rather than frequency as the numbers are more real than the exponential units of frequency IR spectra are observed for what is called the mid-infrared: 400-4000 cm-1 The peaks are Gaussian distributions of the average energy of a transition

IR Spectroscopy

D.

The IR Spectrum 7. In general: Lighter atoms will allow the oscillation to be faster higher energy This is especially true of bonds to hydrogen C-H, N-H and O-H Stronger bonds will have higher energy oscillations Triple bonds > double bonds > single bonds in energy

Energy/n of oscillation

Infrared Spectroscopy

E.

The IR Spectrum The detection of different bonds 7. As opposed to chromatography or other spectroscopic methods, the area of a IR band (or peak) is not directly proportional to concentration of the functional group producing the peak
8. The intensity of an IR band is affected by two primary factors: Whether the vibration is one of stretching or bending Electronegativity difference of the atoms involved in the bond For both effects, the greater the change in dipole moment in a given vibration or bend, the larger the peak. The greater the difference in electronegativity between the atoms involved in bonding, the larger the dipole moment

Typically, stretching will change dipole moment more than bending

Infrared Spectroscopy

E.

The IR Spectrum The detection of different bonds 9. It is important to make note of peak intensities to show the effect of these factors:
Strong (s) peak is tall, transmittance is low (0-35 %) Medium (m) peak is mid-height (75-35%) Weak (w) peak is short, transmittance is high (90-75%) * Broad (br) if the Gaussian distribution is abnormally broad (*this is more for describing a bond that spans many energies) Exact transmittance values are rarely recorded

Infrared Spectroscopy

II.

Infrared Group Analysis A. General 1. The primary use of the IR spectrometer is to detect functional groups
2. Because the IR looks at the interaction of the EM spectrum with actual bonds, it provides a unique qualitative probe into the functionality of a molecule, as functional groups are merely different configurations of different types of bonds Since most types of bonds in covalent molecules have roughly the same energy, i.e., C=C and C=O bonds, C-H and N-H bonds they show up in similar regions of the IR spectrum Remember all organic functional groups are made of multiple bonds and therefore show up as multiple IR bands (peaks)

3.

4.

Infrared Spectroscopy

II.

Infrared Group Analysis A. General 5. The four primary regions of the IR spectrum
Bonds to H O-H single bond N-H single bond C-H single bond Triple bonds CC CN Double bonds C=O C=N C=C Single Bonds C-C C-N C-O Fingerprint Region

4000 cm-1

2700 cm-1

2000 cm-1

1600 cm-1

400 cm-1